Water-insoluble azo dyestuffs



'Patented Mar. 12, 1940 UNITED STATES WATER-INSOLUBLE AZO DYESTUFFS FriedrichWilhelm Muth, Leverkusen-I. G.-Werk, Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application April 5, 1938, Serial No. 200,076. In Germany April 12, 1937 12 Claims.

The present invention relates to new waterinsoluble azodyestufis and to fibers dyed with the new dyestuffs; more particularly, it relates towater-insoluble azodyestuffs obtainable from amides of 3-hydroxy-fiuorene-2-carboxylic acids.

My new coupling components are obtainable by converting 3-hydroxyfiuorene-2-carboxylic acids having a free 4-position or the functional derivatives thereof into the amides of aromatic Oi or heterocyclic monoor diamines. These can be effected by starting from the halides or esters of the said carboxylic acids and causing the same to react with aromatic or heterocyclic mono- .or diamines or by reacting aromatic or heterocyclic isocyanic acid esters with the 3-hydroxy-fluorene 2-carboxylic acids. The 3-hydroxy-2-carboxylic acids which serve as starting materials for the above process can be obtained according to my copending application Ser. No. 200,128 of even date and titled: Ortho-hydroxy carboxylic acids.

The new amides may be substituted in that benzene nucleus of the fiuorene which does not bear the hydroxy group and the carboxylic acid amide group. Assubstituents may be mentioned alkyl, alkoxy, nitro, halogen, trifiuoromethyl,

phenylamino, alkylsulfone, aralkylsulfone, aryl-' sulfone, alkyl-CO'-,' aryl-CO- and so on; also a further nucleus may be condensed to the mentioned benzene nucleus of the fiuorene, forming in this way, for instance, a naphthalene ring system or, in case the nucleus condensed to the fiuorene is hydrogenated, a tetrahydronaphthalene ring system. Such substituted amides can 0 be obtained e. g. from the following 3-hydroxyfluorene-2-carboxylic acids: the methyl-3-hydroxy-fluorene-2-carboxylic acids, the chloro-3- hydroxyfiuorene-2-carboxylic acids, the methoxy-3-hydroxyfiuorene-Z-carboxylic acids, which bear the substituent in question in one of the positions '5, 6, 7 or 8; further the benzo-3-hydr0xyfluorene-2-carboxylic acids having the benzene nucleus condensed to the positions 5.6, 6.7 or 7.8 and also the corresponding tetrahydroacids.

My new amides show in comparison with other amides derived from multinuclear o-hydroxycarboxylic acids a good solubility; thus they dissolve in general already in hot aqueous lyes. 0 They are distinguished by a very good affinity towards cellulosic fibers and by a good coupling energy.

Now it has been found that the new amides not only have a good aflinity to the cellulosic fiber which is one essential prerequisite for the formation of azodyestufis on the fiber, but are also ableto combine with diazo compounds to? azo dyestuffs of valuable and unexpected prop-- erties.

The new dyestuffs are obtainable by diazotizing in the usual manner a primary amine suitable for preparing azodyestufls and coupling in substance or on a substratum, especially on the cellulosic fiber with the above described amides of 3-hydroxyfiuorene-2-carboxylic acids. -Since 10 these new dyestuffs are to be water insoluble, the components are chosen in such a manner that they are free from water solubilizing groups; Depending on the components employed the azo-" dyestuffs thus formed exhibit various shades, particularly khaki to olive-khaki shades, which; when produced on the fiber, are distinguished by excellent fastness properties.

The following examples illustrate the invention, without however restricting it thereto, the parts being by weight: j

Example 1 O on V CONEQ is obtained in short monosymmetrical prisms having a melting point of 176-1'77 C. v

The arylamide obtained in an analogous'manner with 1-amino-2.5-dimethoxybenzene has the, following formula:

OBE

OOHs

OCHs

parts of phosphorus trichloride 25 and crystallizes from toluene in yellow needles of M. P. 186-187 C.

In the following table the melting points are given of further amides of 3-hydroxyfiuorene- 2-carboxylic acid with amines such as Melting-point C. Aniline 246 2-to1uidine 11 211 3-toluidine 1 232 4-toluidine 11 265 2-aminoethylbenzene 11 168 2-anisidine 177 3-anisidine 11 213 4-anisidine 2-phenetidine 11 168 3-ch1oroaniline 233 4-chloroaniline 11 284 3-fiuoroaniline 11 244 3-aminobenzotrifiuoride 11 225 3-nitroaniline 11 288 1-amino-2.3-dimethylbenzene 1 230 1-amino-2.4-dimethylbenzene 11 206 1-amino-2.5-dimethylbenzene 169 1-amino-3.4-dimethylbenzene 227 1-amino-3.5-dimethylbenzene 11 207 1-amino-2-methyl-4-methoxybenzene 228 1amino-2-methyl-5-methoxybenzene 160 l-amino-3-methyl-4-methoxybenzene 200 1-amino-3-methyl6methoxybenzene 1 210 l-amino-4-methyl-3-methoxybenzene 11 202 1-amino-2'-methyl-4-chlorobenzene 236 1-amino-2-methyl-5-chlorobenzene- 238 l-amino-2.4-dimethoxybenzene 153 1-amino-2.5dimethoxybenzene 11 187 1-amino2-methoXy-4-chlorobenzene 232 1-amino-2-methoxy-5chlorobenzene 11 215 1-amino-4-methoxy-3chlorobenzene 230 1-amino-2.4-dimethoxy5chlor0benzene 1 249 1-amino-2.5-dimethoxy-4-chlorobenzene1 1 232 1-amino-2-methoxy- 5 methyl-4-chlor0benzene 212 Z-naphthylamine 270 a-Tetrahydronaphthylamine 11 205 Dianisidine (with 2 mols acid) more than 300 In the same Way the amides of substituted 3-hydroxy-fiuorene-2-carboxylic acids are obtained. 6-methyl-3-hydroXy-fluorene-2-carbox ylic acid yields, with Z-anisidine, the product of which melts at 172 C. The corresponding amides with Oll C. 2-to1uidine 1 has the melting-point1 217 1-amino-2.5-dimethoxybenzene 1 has the melting-point11 189 1amino-2.5-dimethoxyl-chlorobenzene 11has the melting-point11 206 and the 6.7-benzo-3-hydroxyfiuorene-2-carboxylic acid yields, with Z-anisidine, an amide of the formula which melts at 210 C., and with l-amino-2.5- dimethoxybenzene, an amide of the melting-point 230 C.

Example 2 Cotton yarn'is heated at 30 C. for hour with a solution containing per litre 3 parts of 1'-( 3 hydroxyfluorene 2 carboylamino 2'- methoxybenzene, 10 parts of caustic soda lye of 34 B. and a protective colloid. The yarn is freed from the liquid and the dyestufi is then developed for hour in a diazo solution which contains 2.85 parts per litre of l-amino-Z-methoxy-benzene-5-sulfodiethylamide and excess sodium acetate; then the yarn is rinsed and soaped. Strong greenish khaki shades of good boiling properties and fastness to chlorine are thus obtained. It is remarkable that the shades obtained in this manner are not changed when soaped.

In the following table there are mentioned further dyestuffs and shades which have been obtained in accordance with the said method of working:

Coupling component Diazo component Shade 1' (3 hydroxyfluorene 2 carboylamino) 2 methoxivsbenzcnc.

Do 1. l (3 hydroxyfluorene 2 earboylamino) 2.5 (limethoxybcnzene. S-hygoxyfluorene-2-carboylarnino benzene 1 A 2aminc-4.4-dichlorodiphenylcth 1 l-amin0-2-methoxyhenzenc-S-benzylsulfone .1

1-an1ino-2-n1ethyl-5- chlorohenzcne 1 1 2-amino-l-chloro-diphenylether 1 1 Laminol-benzolyaminofl ehloro-5-methoxybenz l-amino-2-chloro-5-trifluoromcthylbenzcna1 1-amino-2.5-dichlor0bcnzenc 1 1 1-amino-2-Inethoxyhcnzene-S-benzylsulfone1 1-amino-f2-meth0xy-5-chlorobcnzene 4-amino-23-dimethyl-1.1-azobenzene 1 l-amino-2methoxyhenzene-S-sulfodicthylamidc 1 B-chloroaniline 1 l-emin0-2-chloro-5benzotrifiuoride1 1-amino-2-mcthyl-fi-nitrobenzene 1-amino2-methyl-3-chlorobenzene 1-amino-2-methyli-chlorobenzenc1 1-amino-2-methyl-5-chlorohenzenc1 1 1 1 l-amino-2-mcthoxy-5-chlorobenzene I-amindZ-methoxy-benzcnc-5-benzylsulfone 2-arnino-4-chlorodiphenylether. 1

Lamino-2-methy1-5-nitrobenzene .1

4 amino 2.4 dimothyl 2 nitro 5 mcthoxy 1.1

azobenzene.

1-amin0-2-methyl-5-nitrobenzenc 11 l-arnino-Z-methyl-S-chlorobenzene 1 1 1 1-amino-2-chloro-5-benzotrifluoride Khaki.

Ycllowish brown.

Orange brown.

. Khaki.

Yellowish brown. 1 Greenish khaki.

Kh akl.

Brown. Greenish khaki.

Yellow olive.

1 Yellowish. 1 Greenish khaki.

Olive brown. Yellowish khaki.

Brownolive. 1 Browmsh olive.

Greenish khaki. BIOWDlSh olive.

0. Yellowish khaki.

Khaki.

D0. Olivish brown. Khaki. Dark-brown.

Grcenish khaki.

1 Khaki 1 Olive.

Do. Greenish khaki.

B-nitroanilinc l-amino-2-methyI-5-chlorobenzene Coupling component I Diazo component Shade 1'-(3-hydroxyfluorene-Z-carboylamino)-3-chloro-4'- l-amino-2-methyl-5-nitrobenzene Grecnish khaki.

methoxybenzene.

1-amino-2-methoxy-B-nitrobenzene. Do. l-amino-2-mcthyl-5-ch1orobenzene Khaki. l-amino-2-methoxy-5-chlorobenzen Brownollve. D0 1-amino-2-chloro-5-benzotrifluoride Yellow-olive. 1-(ii-hydroxyfluorene-Z-carboylamino 3ch1oroani1ine Khaki.

5-chlorobenzene.

2 nitroaniline r Olive-brown. 1amino-2-methoxy-5-nitrobenzen aki. l-amino-2-methoxy-5-chlorobenzen Greenish khaki. 1-amino-2-methoxy benzene-5-sulfodiethylam Khaki. l-amino-2-methoxybenzcne-5-benzylsulfone Olivish khaki. 2-amino-4-chlorodiphenylether.; Khaki. l-amino-2-methoxy-5-nitrobenzene.. Do.

1-a1nino-2-mcth0xy benzene-5-sulfodiethylamide Do. l-amino-2-methoxybeuzene-dbenzylsulfone D0. l-amino-Z-chlorobenzene-5-benzotrifluoride Yellowish brown. Z-amino-4-chlorodiphenylcther Olive-brown. -2-nitroaniline Khaki.

1-amino-2-methoxybenzene-5-sulfodiethylam1de. Khaki. 1-amino-2 methoxyhenzene-Sethylsulfone Do. l-a1nino-Z-rnethoxybenzene-S-benzylsulfone. Do. 2-chloroaniline Yellowish khaki.

2.5-dichlornani Olivish brown. 3-nitroaniline Yellowish khaki. 1-amino-2-chloro-5-benzotrifluoride Olivish brown. 1 amino-2-methyl-5-nitrobenzene. Khaki. 1-amino-2-methoxy-5-nitrobenzene Greenish khaki. l-amino-Z-methyl-li-chlorobenzene Yellowish khaki. l-amino-2-methoxybenzene-fi-sulfodiethylamide Khaki. A 1-amino-2-methoxybenzene-5-ethy1sulfone Greenish khaki. O-amino-azotoluene Dark brown. 1-amino-2-methyl-4-ch1orobenzene Yellow olive.

Lamina-2 methyl-fi-chlorobenzene Yellowish khaki. 1 -amino-2-methoxy-5-nitrobenzone. Brown olive.

1-amino-2.5-dichlorobenzene 1-amino-3.5-di(trifluoromethyl)-benzene.

Yellow brown. Yellowish brown.

2-amino-4,4-dichlorodiphenylether Olive brown.

Similar shades are obtained when using the amides of substituted 3-hydroxyfluorene-2-carboxylic acids:

Coupling component Diazo component sh 1'-(6- methyl 3 hydroxy fiuorene 2 carboylamino)- Z-chloroaniline Yellowish khaki.

2 582????2? Lamina-kmethyl-E-nitrobenzene Khak D l-amino-2-methoxy-5-n1trobenzene Brownlsh olive. Do 1-amino-2-methoxy-benzene-5-benzylsulfone. Ol ve brown.

D l-amino-2-methoxy-benzene-fi-sulfodlethylamide, OIIVB brown. 1-(6-methyl-3-hydroxy-fluorene-2-carboylamino)- 1-amino-Z-methoxy-fi-mtrobenzone Green olive.

2 b g ffi iif ffii 1-amino-2-n1ethoxy-benzene-5-benzylsulfone Do.

Do 1-amino-Z-methoxy-benzene-fi-sulfodiethyl-amide. Gteenish khaki. 1'-(6 ethyl 3 hydroxy fluorene 2 carboylamino)- 1-amino-2-methy1-4-c 0 benzene Yellow olive.

/ I I V 2 Jndlmethoxybenzene l-amino-2-methoxy-5-nitto-benzene Olive brown. Do I-amino-Z-methoxy benzene-6-benzylsulfone. Greon sh khaki. Do l-amino-2-methoxybenzene-fi-ethylsplfone. Khaki.

D0 1-amino-z-inethoxybenzene-5-sulfod1ethylamide Do. 1-(6.7 benzo 3 hydroxyfluorene 2 carboylamino)- 2-chloroani1me Yellowish brown.

2 i thoxybenzene. 1-amino-2-chloro-5-w-trifluoro-methylbenzene Brown. D 1-amino-4-ch10t0-2-w-tlifluoro-methylbenzene Do, Do l-amino-2-methoxy-5-nitrobenzone OhVISh dark brown. Dn l-amino-2-methoxy-benzenesulfodxethylamrde Do. Do 1-amino-2-methoxy-benzene-fi-benzyl-sulfone Do.

I claim: 2. Water insoluble azodyestufis of the general 1. Water insoluble azodyestufis of the general formula formula N=NR N=N-R' OH OH X y CHa CO.NH.R

00 N wherein R'-N=N stands for the radical of an wherein R and R stand for aromatic radicals and X stands for one of the group consisting of the benzene nucleus, the alkyl substituted benzene nucleus and the naphthalene nucleus, yielding, when produced on the fiber, shades of good fastness properties.

aromatic diazo compound suitable for producing water insoluble azodyestufis, R stands for a radical of the benzene series, and X stands for one of the group consisting of the benzene nucleus, th alkyl substituted benzene nucleus and the naphthalene nucleus, yielding, when produced on the fiber, shades of good fastness properties.

3. Water insoluble azodyestufis of the general formula wherein R. and R stand for radicals of the henzene series and X stands for one of the group consisting of the benzene nucleus, the alkyl substituted benzene nucleus and the naphthalene nucleus, yielding, when produced on the fiber, shades of good fastness properties.

4. The water insoluble azodyestufi of the formula:

dyeing the cellulosic fiber greenish khaki shades of good fastness properties.

5. The water insoluble dyestufi of the formula CH2 0 o .NHQ

dyeing the cellulosic fiber yellowish khaki shades of good fastness properties.

6. The water insoluble dyestufi of the formula -0H CH3 l \CONHOCI 

